EP1084826A1 - Précurseur pour plaque lithographique thermosensible - Google Patents

Précurseur pour plaque lithographique thermosensible Download PDF

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Publication number
EP1084826A1
EP1084826A1 EP00119409A EP00119409A EP1084826A1 EP 1084826 A1 EP1084826 A1 EP 1084826A1 EP 00119409 A EP00119409 A EP 00119409A EP 00119409 A EP00119409 A EP 00119409A EP 1084826 A1 EP1084826 A1 EP 1084826A1
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EP
European Patent Office
Prior art keywords
printing plate
plate precursor
heat
layer
ink
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00119409A
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German (de)
English (en)
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EP1084826B1 (fr
Inventor
Nobuyuki Kita
Keiji Akiyama
Hidekazu Oohashi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication date
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Publication of EP1084826A1 publication Critical patent/EP1084826A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/02—Cover layers; Protective layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/14—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by macromolecular organic compounds, e.g. binder, adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/08—Developable by water or the fountain solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/165—Thermal imaging composition

Definitions

  • the present invention relates to a heat-sensitive lithographic printing plate precursor which requires no development processing and is excellent in press life and resistance to staining. More specifically, the present invention relates to a lithographic printing plate precursor capable of image-recording by an infrared ray or near infrared ray laser beam scanning exposure based on digital signals, and a lithographic printing plate precursor on which the image has been recorded can be directly loaded on a printer (i.e., a printing press) without undergoing development processing and then printing can be effected.
  • a printer i.e., a printing press
  • lithographic printing plate precursor capable of image-forming by heat and directly loadable on a printer without undergoing development processing.
  • One promising method is a method of utilizing abrasion, wherein a lithographic printing plate precursor is subjected to exposure with solid state high output infrared-ray lasers such as a semiconductor laser or a YAG laser to make the irradiated part generate heat with a light-to-heat conversion material, thereby cracking evaporation is caused.
  • this is a method of providing a hydrophilic layer on a lipophilic substrate or a substrate having a lipophilic layer and removing the hydrophilic layer by abrasion.
  • WO 94/18005 discloses a printing plate comprising a laser beam-absorbing lipophilic layer having provided thereon a crosslinked hydrophilic layer, wherein the hydrophilic layer is removed by abrasion.
  • This hydrophilic layer comprises polyvinyl alcohol crosslinked with the hydrolyzate of tetraethoxysilane and titanium dioxide particles contained therein, which intends to improve the strength of the hydrophilic layer.
  • the impression capability of a lithographic printing plate precursor is improved by this technique, however, since the polyvinyl alcohol having hydrocarbon groups and not always having high hydrophilic property accounts for 48 wt% of the hydrophilic layer, the resistance to staining is not still sufficient and further improvement is required.
  • lithographic printing plate precursors directly loadable on a printer without subjecting to development, which comprises a substrate having coated thereon an ink-receptive layer, and a hydrophilic layer comprising, as a main component, a colloid such as silica, crosslinked with a crosslinking agent such as aminopropyltriethoxysilane.
  • This hydrophilic layer contains hydrocarbon groups as small as possible to heighten the resistance to printing staining and is improved in the impression capability by crosslinking the colloid with a crosslinking agent, but the impression capability is several thousands, which is still insufficient.
  • the digital direct processing-free printing plate which utilizes abrasion has big advantages of rationalization of printing and the reduction of wastes such that plate-making can be performed directly from a camera-ready copy without the use of a film, the printing plate can be loaded on a printer as it is and printing can be performed immediately.
  • the difficulty of processing-free technique either the resistance to staining or the impression capability, both of which are fundamentals of the printing, is liable to be damaged, therefore, a technique which makes both compatible has not yet been developed.
  • An object of the present invention is to solve the above object. That is, an object of the present invention is to provide a heat-sensitive lithographic printing plate precursor that can be directly mounted on a printer (i.e., a printing press) without development processing and printing can be performed immediately, is excellent in press life and resistance to printing staining.
  • a printer i.e., a printing press
  • the present inventors have found that, by the development of a novel and superior hydrophilic layer, a heat-sensitive lithographic printing plate precursor which can be directly mounted on a printer without development processing, and is excellent in printing aptitude, in particular, impression capability and resistance to printing staining, can be obtained, thus the present invention has been achieved.
  • the present invention is as follows.
  • the hydrophilic layer for use in the present invention comprises a colloid of an oxide or a hydroxide of at least one element selected from the group consisting of beryllium, magnesium, aluminum, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony and transition metals, a hydrophilic resin, and a light-to-heat conversion material.
  • the hydrophilic layer according to the present invention is a layer insoluble in a fountain solution in lithographic printing using a fountain solution.
  • colloids are produced by various methods such as hydrolysis of the halides and the alkoxy compounds of the above elements and condensation of the hydroxides of the above elements.
  • the above elements form network structure through oxygen atoms and at the same time have non-bonded hydroxyl groups and alkoxy groups and they form mixed structure.
  • Many active alkoxy groups and hydroxyl groups are contained in the initial stage of hydrolysis and condensation and particle diameters become large and active groups become inactive as the reaction progress.
  • the particle size of the colloid is in general from 2 to 500 nm, and in the case of silica, spherical particles having a particle diameter of from 5 to 100 nm are preferably used in the present invention.
  • Pearl neck-like colloids in which spherical particles having particle diameters of from 10 to 50 nm lie in a row in a length of from 50 to 400 nm can also be used.
  • plume-like colloids of 100 nm ⁇ 10 nm such as aluminum colloids are also effectively used.
  • hydrophilic resins for use in the hydrophilic layer according to the present invention resins having a hydrophilic group, such as hydroxyl, carboxyl, hydroxyethyl, hydroxypropyl, amino, aminoethyl, aminopropyl, and carboxymethyl are preferred.
  • hydrophilic resins include gum arabic, casein, gelatin, starch derivatives, carboxymethyl cellulose, and Na salts thereof, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, homopolymers and copolymers of hydroxypropyl methacrylate, homopolymers and copolymers of hydroxypropyl acrylate, homopolymers and copolymers of hydroxybutyl methacrylate, homopolymers and copolymers of hydroxybutyl acrylate, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, hydrolyzed polyvinyl acetate having a hydrolysis degree of at least 60 w
  • Particularly preferred hydrophilic resins are hydroxyl group-containing polymers, specifically homopolymers and copolymers of hydroxyethyl acrylate and hydroxyethyl methacrylate.
  • the proportion of the addition amount of these hydrophilic resins is preferably from 0.1 to 30 wt%, particularly preferably from 5 to 20 wt%, based on the entire solid content of the hydrophilic layer.
  • the addition amount is less than this range, impression capability is insufficient, and when it exceeds this range, printing staining is liable to occur.
  • the light-to-heat conversion materials to be added to the hydrophilic layer according to the present invention for increasing heat sensitivity substances which absorb light of the wavelength of 700 nm or more may be used and various pigments and dyes can be used as the light-to-heat conversion materials.
  • various pigments and dyes can be used as the light-to-heat conversion materials.
  • pigments e.g., black pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metallic powder pigments, and polymer-attaching pigments can be exemplified.
  • insoluble azo pigments azo lake pigments, condensation azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene pigments, perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, in-mold lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, and carbon black can be used.
  • These pigments may be used without surface treatment or may be surface-treated.
  • methods of surface treatments a method of surface-coating with hydrophilic resins and lipophilic resins, a method of adhering surfactants, and a method of attaching reactive substances (e.g., silica sol, alumina sol, silane coupling agents, epoxy compounds, isocyanate compounds, etc.) on the surfaces of pigments can be exemplified.
  • reactive substances e.g., silica sol, alumina sol, silane coupling agents, epoxy compounds, isocyanate compounds, etc.
  • These surface treatment methods are described in Kinzoku Sekken no Seishitsu to Oyo (Natures and Applications of Metal Soaps) , Saiwai Shobo Co., Ltd., Insatsu Ink Gijutsu (Printing Ink Technique) , CMC Publishing Co., Ltd.
  • pigments those which absorb infrared rays or near infrared rays are particularly preferred as they are suitable for use of lasers emitting infrared rays or near infrared rays.
  • pigments which absorb infrared rays and near infrared rays carbon black, carbon black coated with a hydrophilic resin, and carbon black modified with a silica sol are preferably used.
  • carbon blacks surface-coated with a hydrophilic resin or a silica sol are particularly preferred because they are easily dispersible with water-soluble resins and the hydrophilicity is not impaired.
  • the particle size of pigments is preferably from 0.01 to 1 ⁇ m, more preferably from 0.01 to 0.5 ⁇ m.
  • Well-know dispersing methods used in the manufacture of inks and toners can be used as dispersing methods of pigments.
  • Examples of dispersing apparatus include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super-mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, a pressure kneader, etc., and details are described in Shaishin Ganryo Oyo Gijutsu (The Latest Pigment Applied Technique) , CMC Publishing Co., Ltd. (1986).
  • Dyes for use as a light-to-heat conversion material include commercially available dyes and well-known dyes described, for example, in Senryo Binran (Dye Handbook) , compiled by Yuki Gosei Kagaku Kyokai (1970). Specifically, azo dyes, metal complex azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, and cyanine dyes can be used. Of these dyes, those which absorb infrared rays or near infrared rays are particularly preferred as they are suitable for use of lasers emitting infrared rays or near infrared rays.
  • JP-A-58-125246 As dyes which absorb infrared rays or near infrared rays, e.g., the cyanine dyes disclosed in JP-A-58-125246 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), JP-A-59-84356, and JP-A-60-78787, the methine dyes disclosed in JP-A-58-173696, JP-A-58-181690, and JP-A-58-194595, the naphthoquinone dyes disclosed in JP-A-58-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, and JP-A-60-63744, the squarylium dyes disclosed in JP-A-58-112792, the cyanine dyes disclosed in British Patent 434,875, the dyes disclosed in U.S.
  • the near infrared ray-absorbing sensitizing dyes disclosed in U.S. Patent 5,156,938 are also preferably used as the dye.
  • the substituted arylbenzo(thio)pyrylium salts disclosed in U.S. Patent 3,881,924, the trimethine thiapyrylium salts disclosed in JP-A-57-142645 (corresponding to U.S.
  • Patent 4,327,169 the pyrylium-based compounds disclosed in JP-A-58-181051, JP-A-58-220143, JP-A-59-41363, JP-A-59-84248, JP-A-59-84249, JP-A-59-146063, and JP-A-59-146061, the cyanine dyes disclosed in JP-A-59-216146, the pentamethine thiopyrylium salts disclosed in U.S.
  • Patent 4,283,475 the pyrylium compounds disclosed in JP-B-5-13514 (the term "JP-B” as used herein means an "examined Japanese patent publication") and JP-B-5-19702, Epolight III-178, Epolight III-130, and Epolight III-125 (manufactured by Epolin Co., Ltd.) are particularly preferably used. Of these dyes, specific examples of particularly preferred dyes are shown below in structural formulae.
  • the proportion of the pigment or the dye is from 1 to 50 wt%, preferably from 2 to 20 wt%, of the total weight of the colloid and the hydrophilic resin.
  • a crosslinking agent for accelerating the crosslinking of colloid can be added to the hydrophilic layer of the present invention.
  • An initial hydrolysis condensation product of tetraalkoxysilane, trialkoxysilylpropyl-N,N,N-trialkylammonium halide and aminopropyltrialkoxysilane are preferably used.
  • the addition amount of crosslinking agents is preferably 5 wt% or less of the entire solid content of the hydrophilic layer.
  • crosslinking agents for hydrophilic resins can be added to the hydrophilic layer according to the present invention.
  • crosslinking agents for hydrophilic resins formaldehyde, glyoxal, polyisocyanate, an initial hydrolysis condensation product of tetraalkoxysilane, dimethylolurea and hexamethylolmelamine can be exemplified.
  • fluorine-based surfactants silicon-based surfactants, polyoxyethylene-based surfactants, etc.
  • silicon-based surfactants silicon-based surfactants, polyoxyethylene-based surfactants, etc.
  • the coating thickness of the hydrophilic layer according to the present invention is preferably from 0.1 to 3 ⁇ m, more preferably from 0.5 to 2 ⁇ m.
  • the coating thickness of the hydrophilic layer according to the present invention is preferably from 0.1 to 3 ⁇ m, more preferably from 0.5 to 2 ⁇ m.
  • a thickness of about 0.5 ⁇ m requires energy of from 300 to 400 mJ/cm 2 and a thickness of about 1.5 ⁇ m requires energy of from 400 to 500 mJ/cm 2 .
  • Dimensionally stable plate-like substances are used as the substrate having an ink-receptive surface or coated with an ink-receptive layer for use in the present invention, e.g., paper, paper laminated with lipophilic plastics (e.g., polyethylene, polypropylene, polystyrene, etc.), metal plates (e.g., aluminum, zinc, copper, nickel, stainless steel plates, etc.), plastic films (e.g., cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper or plastic films laminated or deposited with the above metals.
  • plastics e.g., polyethylene, polypropylene, polystyrene, etc.
  • metal plates e.g., aluminum, zinc, copper, nickel, stainless steel plates, etc
  • Preferred substrates are polyethylene terephthalate films, polycarbonate films, aluminum or steel plates, and aluminum or steel plates laminated with lipophilic plastic films.
  • Aluminum plates of conventionally well-known materials can be arbitrarily used in the present invention.
  • Aluminum plates are preferably subjected to surface roughening treatment before use.
  • surface roughening treatment By surface roughening treatment, the adhesion of the ink-receptive layer comprising an organic high polymer with the substrate can be ensured.
  • Well-known surface roughening treatments of aluminum plate can be used in the present invention.
  • the organic high polymers to be coated on the surface of the substrate of the present invention as an ink-receptive layer are those which are soluble in a solvent and capable of forming a lipophilic film. Further, these organic high polymers are preferably insoluble in the coating solvent of the upper hydrophilic layer, but sometimes it is preferred that the organic high polymers are partially swollen in the coating solvent of the upper hydrophilic layer in view of the adhesion with the upper layer. Moreover, when organic high polymers which are soluble in the coating solvent of the upper layer are used, it is preferred to contrive to add a crosslinking agent and so on to harden the polymers in advance.
  • Examples of useful organic high polymers for use in the present invention include polyester, polyurethane, polyurea, polyimide, polysiloxane, polycarbonate, a phenoxy resin, an epoxy resin, a phenol-formaldehyde resin, an alkylphenol-formaldehyde resin, polyvinyl acetate, an acrylate resin and copolymers thereof, polyvinyl phenol, polyvinyl halogenated phenol, a methacrylate resin and copolymers thereof, an acrylamide copolymer, a methacrylamide copolymer, polyvinyl formal, polyamide, polyvinyl butyral, polystyrene, a cellulose ester resin, polyvinyl chloride and polyvinylidene chloride.
  • resins having a hydroxyl group, a carboxyl group, a sulfonamido group or a trialkoxysilyl group at the side chain are more preferred because they are excellent in adhesion with the substrate or the upper hydrophilic layer and in some cases they are easily hardened with a crosslinking agent.
  • acrylonitrile copolymers, polyurethane, copolymers having a sulfonamido group at the side chain and copolymers having a hydroxyl group at the side chain which are photopolymerized (i.e., photo-hardened) with a diazo resin are preferably used.
  • novolak resins and resol resins of condensation with formaldehyde such as, cresol (m-cresol, p-cresol, m/p mixed cresol) , phenol/cresol (m-cresol, p-cresol, m/p mixed cresol), phenol-modified xylene, tert-butylphenol, octylphenol, resorcinol, pyrogallol, catechol, chlorophenol (m-Cl, p-Cl), bromophenol (m-Br, p-Br), salicylic acid, and fluoroglucinol, and condensation resins of the above phenol compounds with acetone are useful in the present invention.
  • formaldehyde such as, cresol (m-cresol, p-cresol, m/p mixed cresol) , phenol/cresol (m-cresol, p-cresol, m/p mixed cresol), phenol-modified xylene, tert-but
  • copolymers with the monomers shown in (1) to (12) below as repeating units and have molecular weight of generally from 10,000 to 200,000 can be exemplified.
  • the ink-receptive layer can be provided by dissolving these organic high polymers in an appropriate solvent and coating them on a substrate and then drying.
  • Organic high polymers may be dissolved in a solvent alone but, if necessary, a crosslinking agent, an auxiliary adhesive (i.e., an adhesion aid), a coloring agent, inorganic or organic fine particles, a coating surface improving agent, or a plasticizer can be added.
  • a light-to-heat conversion material for improving heat sensitivity and a heat-color forming compound or a decoloring compound for forming printout images after exposure may be added to the ink-receptive layer.
  • crosslinking agents for crosslinking organic high polymers include diazo resins, aromatic azido compounds, epoxy resins, isocyanate compounds, block isocyanate compounds, initial hydrolysis condensation product of tetraalkoxysilane, glyoxal, aldehyde compounds and methylol compounds.
  • the above-described diazo resins are superior in adhesion with the substrate and the hydrophilic layer, in addition, silane coupling agents, isocyanate compounds, titanium coupling agents are also useful.
  • dyes and pigments are used as the coloring agents in the present invention, and preferred examples include Rhodamine 6G chloride Rhodamine B chloride, Crystal Violet, Malachite Green oxalate, oxazine-4-perchlorate, quinizarin, 2-( ⁇ -naphthyl)-5-phenyloxazole, and coumarin-4.
  • Patent Pure Blue manufactured by Sumitomo Mikuni Chemical Co., Ltd.
  • Brilliant Blue Methyl Green, Erythrisine B, Basic Fuchsine, m-Cresol Purple, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, and cyano-p-diethylaminophenyl acetanilide
  • JP-A-62-293247 and JP-A-9-17290 can be exemplified.
  • the proportion is generally preferably from 0.02 to 10 wt%, more preferably from 0.1 to 5 wt%, based on the entire solid content of the ink-receptive layer.
  • fluorine-based surfactants and silicon-based surfactants which are well known as coating surface improving agents can also be sued.
  • surfactants having a perfluoroalkyl group or a dimethylsiloxane group are useful as they can adjust the coating surface.
  • colloidal silica and colloidal aluminum having a particle size of from 10 to 100 nm, inert particles having a larger particle size than the above colloids, e.g., silica particles, surface-hydrophobitized silica particles, alumina particles, titanium dioxide particles, other metallic particles, clay and talc can be exemplified.
  • silica particles, surface-hydrophobitized silica particles, alumina particles, titanium dioxide particles, other metallic particles, clay and talc can be exemplified.
  • the adhesive property of the ink-receptive layer with the upper hydrophilic layer can be improved and impression capability in printing can be increased.
  • the proportion of these fine particles is 80 wt% or less, preferably 40 wt% or less, of the total amount of the ink-receptive layer.
  • Plasticizers are added to the ink-receptive layer according to the present invention for giving flexibility to the film, if necessary.
  • plasticizers e.g., polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic acid or methacrylic acid, etc., are used.
  • color-forming or decoloring compounds are preferably added to the ink-receptive layer according to the present invention for discriminating between an image area and a non-image area after exposure.
  • leuco dyes Leuco Malachite Green, Leuco Crystal Violet, and lactone body of Crystal Violet, etc.
  • PH discoloring dyes e.g., Ethyl Violet, Victoria Pure Blue BOH, etc.
  • a heat-acid generating agent such as diazo compounds and diphenyl iodonium salts.
  • acid-coloring dyes with acidic binders as disclosed in EP 897134 is also useful. In this case, the bonding of the associated condition forming a dye is cut by heating to from the lactone body and colored state changes to colorless state.
  • the addition amount of these color-forming or decoloring compounds is 10 wt% or less, preferably 5 wt% or less, based on the entire amount of the ink-receptive layer.
  • a light-to-heat conversion material for improving heat sensitivity may further be added to the ink-receptive layer according to the present invention.
  • the light-to-heat conversion material may be the above-described infrared-absorbing dyes and pigments, but in this case, lipophilic dyes and pigments are preferably used. Carbon black and lipophilic cyanine dyes are particularly preferably used. Specific examples of lipophilic cyanine dyes are shown below.
  • the proportion (of the addition amount) of light-to-heat conversion materials to the ink-receptive layer is preferably 20 wt% or less, more preferably 15 wt% or less, based on the entire amount of the ink-receptive layer.
  • the addition amount of pigments or dyes exceeds the above range, the durability of the ink-receptive layer is deteriorated.
  • alcohols e.g., methanol, ethanol, propyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.
  • ethers e.g., tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetrahydropyran, etc.
  • ketones e.g., acetone, methyl ethyl ketone, acetylacetone, etc.
  • esters e.g., methyl acetate, ethylene glycol monomethyl monoacetate, etc.
  • amides e.g., formamide, N-methylformamide, pyrrolidone, N-methylpyrrolidone, etc.
  • ⁇ -butyrolactone methyl lactate
  • the concentration of the constitutional component of the ink-receptive layer (the entire solid content exclusive of additives) in a solvent is preferably from 1 to 50 wt%.
  • the film can be formed not only by coating from the organic solvent but also from aqueous emulsion. In this case, the concentration of the component of the ink-receptive layer is preferably from 5 wt% to 50 wt%.
  • the dry coating thickness of the ink-receptive layer according to the present invention is not particularly limited and the thickness of 0.1 ⁇ m or more should be sufficient.
  • the thickness of 0.5 ⁇ m or more is preferred since the layer also functions as a heat-insulating layer. If the thickness of the ink-receptive layer is too thin, generated heat is dispersed to the metal plate and the sensitivity is lowered. Moreover, if the metal plate is hydrophilic, abrasion resistance is required for the ink-receptive layer, hence impression capability cannot be ensured.
  • the coating amount may be smaller than that in the case of the metal plate, preferably 0.05 ⁇ m or more.
  • An overcoat layer comprising a water-soluble resin may be provided on the hydrophilic layer of the heat-sensitive lithographic printing plate precursor of the present invention for the purpose of inhibiting the scattering of chips (i.e., tailings) due to abrasion and preventing the hydrophilic layer from being stained by lipophilic substances.
  • the water-soluble overcoat layer for use in the present invention can be easily removed at printing and contains resins selected from water-soluble organic or inorganic high molecular compounds.
  • the water-soluble organic or inorganic high molecular compounds should have film-forming ability by coating and drying.
  • high molecular compounds include polyvinyl acetate (hydrolysis factor of 65% or more), polyacrylic acid and alkali metal salts or amine salts thereof, polyacrylic acid copolymer and alkali metal salts or amine salts thereof, polymethacrylic acid and alkali metal salts or amine salts thereof, polymethacrylic acid copolymer and alkali metal salts or amine salts thereof, polyacrylamide and copolymers thereof, polyhydroxyethyl acrylate, polyvinyl pyrrolidone and copolymers thereof, polyvinyl methyl ether, polyvinyl methyl ether-maleic anhydride copolymers, poly-2-acrylamide-2-methyl-1-propanesulfonic acid and alkali metal salts or amine salts thereof, poly-2-acrylamide-2-methyl-1-propanesulfonic acid copolymer and alkali metal salts or amine salts thereof, gum arabic, cellulose derivatives (e.g., poly
  • nonionic surfactants can be added to the overcoat layer in the case of coating an aqueous solution for the purpose of ensuring coating uniformity.
  • nonionic surfactants sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylenenonylphenyl ether, and polyoxyethylenedodecyl ether can be exemplified.
  • the proportion of the nonionic surfactants in the entire solid content of the overcoat layer is preferably from 0.05 to 5 wt%, more preferably from 1 to 3 wt%.
  • a light-to-heat conversion material for improving heat sensitivity may further be added to the overcoat layer according to the present invention.
  • Light-to-heat conversion materials which can be added to the overcoat layer may be the above-described infrared ray-absorbing dyes or pigments, but water-soluble cyanine dyes which are suitable for the hydrophilic layer are preferably used.
  • the amount of pigments or dyes is from 1 to 70 wt%, preferably from 2 to 50 wt%, of the entire solid content of the overcoat layer, in the case of dyes, the proportion (of the addition amount) is particularly preferably from 2 to 30 wt%, and in the case of pigments, particularly preferably from 20 to 50 wt%. Since a light-to-heat conversion material is added to the hydrophilic layer in the present invention, the addition amount to be added to the overcoat layer according to necessity can be reduced.
  • the overcoat layer according to the present invention preferably has a thickness of from 0.05 to 4.0 ⁇ m, more preferably from 0.1 to 1.0 ⁇ m.
  • a water-soluble resin dissolved in a large amount influences a fountain solution, as a result, bad influences are caused such that roller strip may be generated at printing or ink does not adhere to the image area.
  • a film property is impaired in some cases.
  • An image is formed by heating on the lithographic printing plate precursor according to the present invention. Specifically, an image is recorded by direct image-drawing with a heat-recording head, scanning exposure with an infrared laser, high intensity flash exposure by a xenon discharge lamp, etc., and infrared lamp exposure. Exposure by solid state high output infrared lasers such as semiconductor lasers emitting infrared rays of wavelength of from 700 to 12,000 nm and YAG lasers is preferred in the present invention.
  • Image-exposed lithographic printing plate precursor according to the present invention can be loaded on a printer (i.e., a printing press) without necessitating any further process.
  • a printer i.e., a printing press
  • the overcoat layer is removed by the fountain solution and at the same time the hydrophilic layer at the exposed area is also removed, ink adheres to the ink-receptive layer under the hydrophilic layer and printing begins.
  • V-65 a product of Wako Pure Chemical Co., Ltd.
  • V-65 a product of Wako Pure Chemical Co., Ltd.
  • anodic oxidation treatment and sodium silicate solution treatment was coated a coating solution comprising 3 g of the above N-(p-aminosulfonylphenyl)methacrylamide copolymer, 9.5 g of ⁇ -butyrolactone, 3 g of methyl lactate, 22.5 g of methyl ethyl ketone, and 22 g of propylene glycol monomethyl ether.
  • the coating solution was coated by a bar coater so that the coating amount of the solution became 24 ml/m 2 .
  • the aluminum plate was dried by heating at 100°C for 1 minute, thereby an aluminum substrate with an ink-receptive layer having a dry coating weight of about 1 g/m 2 was obtained.
  • a coating solution comprising 1 g of a 10% ethylene glycol monomethyl ether solution of poly-2-hydroxyethyl methacrylate (weight average molecular weight: 250,000), 3 g of methanol silica (manufactured by Nissan Chemical Industries, Ltd., colloid comprising a methanol solution containing 30 wt% of silica particles having a particle diameter of from 10 to 20 nm), 0.08 g of Cyanine Dye (I-33), and 16 g of methanol was coated on the above-coated ink-receptive layer provided on the aluminum substrate, and dried at 100°C for 1 minute to thereby provide a hydrophilic layer having a dry coating weight of about 1 g/m 2 on the ink-receptive layer.
  • the above lithographic printing plate precursor was attached to 40 W Trend Setter (a plate setter loading a semiconductor laser of 830 nm, 40 W, manufactured by CREO Co., Canada) and exposure was performed by energy of 300 mJ/cm 2 .
  • the exposed printing plate precursor was loaded on Harris printer without any further process.
  • printing was performed using ink and a fountain solution comprising a 10 vol% aqueous isopropyl alcohol solution containing an etching solution, 10,000 sheets of clear printed matters could be obtained.
  • a heat-sensitive lithographic printing plate precursor was prepared in the same manner as in Example 1 except that 4.5 g of Graska 401 (manufactured by Nippan Kenkyu-Jo Co., Ltd., a 20 wt% methanol colloidal solution comprising ZrO 2 ⁇ SiO 2 ) was used in place of 3 g of methanol silica.
  • the printing plate precursor was subjected to exposure in the same manner as in Example 1. When printing was performed with Harris printer, 10,000 sheets of clear printed matters could be obtained.
  • a heat-sensitive lithographic printing plate precursor was prepared in the same manner as in Example 1 except that 1 g of a 10% ethylene glycol monomethyl ether solution of a copolymer (weight average molecular weight: 200,000) of 2-hydroxyethyl methacrylate/methyl methacrylate (70/30 wt%) was used in place of 1 g of a 10% ethylene glycol monomethyl ether solution of 2-hydroxyethyl methacrylate homopolymer.
  • the printing plate precursor was subjected to exposure in the same manner as in Example 1. When printing was performed with Harris printer, 15,000 sheets of clear printed matters could be obtained.
  • a heat-sensitive lithographic printing plate precursor was prepared in the same manner as in Example 1 except that 2 g of a 10% ethylene glycol monomethyl ether solution of a copolymer (weight average molecular weight: 300,000) of 2-hydroxyethyl methacrylate/acrylic acid (90/10 wt%) was used in place of 1 g of a 10% ethylene glycol monomethyl ether solution of 2-hydroxyethyl methacrylate homopolymer.
  • the printing plate precursor was subjected to exposure in the same manner as in Example 1. When printing was performed with Harris printer, 20,000 sheets of clear printed matters could be obtained.
  • a heat-sensitive lithographic printing plate precursor was prepared by coating a hydrophilic layer having the following composition on the substrate having the ink-receptive layer in Example 1.
  • Methanol silica (the same as in Example 1) 4.5 g A 10% ethylene glycol monomethyl ether solution of poly-2-hydroxyethyl methacrylate (the same as in Example 1) 1.5 g Cyanine Dye (I-34) 0.10 g Methanol 16 g
  • the dry coating weight of the hydrophilic layer of this printing plate precursor was 1.5 g/m 2 .
  • the printing plate precursor was attached to the same plate setter used in Example 1 and exposure was performed by energy of 450 mJ/cm 2 .
  • the exposed printing plate precursor was loaded on Harris printer. When printing was performed using ink and a fountain solution comprising a 10 vol% aqueous isopropyl alcohol solution containing an etching solution, 25,000 sheets of clear printed matters could be obtained.
  • An overcoat layer having the following composition was coated on the heat-sensitive lithographic printing plate precursor in Example 1, and the coated layer was dried at 100°C for 2 minutes, thereby a heat-sensitive lithographic printing plate precursor with an overcoat layer having a dry coating weight of 0.6 g/m 2 on the hydrophilic layer was prepared.
  • Polyacrylic acid (weight average molecular weight: 25,000) 1.0 g Polyoxyethylenenonylphenyl ether 0.025 g Water 19 g
  • the printing plate precursor was subjected to exposure in the same manner as in Example 1. According to the observation of the exposed printing plate precursor, the hydrophilic layer is hardly scattered due to abrasion, and it was found that scattering was prevented.
  • printing was performed with Harris printer in the same manner as in Example 1, 10,000 sheets of clear printed matters could be obtained. On the area where fingers touched when the printing plate precursor was attached to the printer, staining of fingerprints were not generated.
  • Example 7 In place of N-(p-aminosulfonylphenyl)methacrylamide copolymer in Example 1, a phenoxy resin (trade name: Phenototo YP-50, manufactured by Toto Kasei Co., Ltd.) was used in Example 7, a polyvinyl formal resin (trade name: Denka Formal #200, manufactured by Electro Chemical Industry Co., Ltd.) was used in Example 8, a polyurethane resin (trade name: Estan #5715, manufactured by Monsanto Co., Ltd.) was used in Example 9, a saturated copolymer polyester resin (trade name: Kemit K-1294, manufactured by Toray Industries Inc., was used in Example 10, and methyl methacrylate/methacryloyloxypropyltriethoxysilane (60/40 wt%) copolymer (average molecular weight: 85,000) was used in Example 11.
  • a phenoxy resin trade name: Phenototo YP-50, manufactured by Toto Kasei Co.,
  • Example 1 The same hydrophilic layer as in Example 1 was coated on each substrate, and the same overcoat layer as in Example 6 was coated on the hydrophilic layer to thereby obtain a heat-sensitive lithographic printing plate precursor.
  • Each printing plate precursor was subjected to exposure in the same manner as in Example 1. When printing was performed with Harris printer, 10,000 sheets of clear printed matters could be obtained.
  • Substrates having an ink-receptive layer containing a light-to-heat conversion material were prepared by replacing the coating solution for the ink-receptive layer in Example 1 with the following composition.
  • Example 1 N-(p-aminosulfonylphenyl)methacrylamide copolymer in Example 1 (the same as in Example 1) 3 g Cyanine dye 0.3 g ⁇ -Butyrolactone 9.5 g Methyl lactate 3 g Methyl ethyl ketone 22.5 g Propylene glycol monomethyl ether 22 g
  • Cyanine Dye (I-36) was used in Example 12
  • Cyanine Dye (I-37) was used in Example 13
  • Cyanine Dye (I-38) was used in Example 14, respectively.
  • Example 5 The same hydrophilic layer as in Example 5 was coated on the above-prepared substrate having the ink-receptive layer in a dry coating weight of about 1.5 g/m 2 , and the same overcoat layer as in Example 6 was coated on the hydrophilic layer, thereby a heat-sensitive lithographic printing plate precursor was obtained.
  • Each printing plate precursor was attached to the same plate setter used in Example 1 and exposure was performed by energy of 400 mJ/cm 2 . When the exposed printing plate precursor was loaded on Harris printer and printing was performed, 25,000 sheets of clear printed matters could be obtained.
  • An overcoat layer having the following composition was coated on the heat-sensitive lithographic printing plate precursor in Example 5 in a dry coating weight of 0.6 g/m 2 , thereby a heat-sensitive lithographic printing plate precursor was prepared.
  • Polyacrylic acid (weight average molecular weight: 25,000) 1.0 g Polyoxyethylenenonylphenyl ether 0.025 g Cyanine Dye (I-31) 0.2 g Water 19 g
  • the printing plate precursor was attached to the same plate setter used in Example 1 and exposure was performed by energy of 400 mJ/cm 2 .
  • exposure was performed by energy of 400 mJ/cm 2 .
  • Harris printer When the exposed printing plate precursor was loaded on Harris printer and printing was performed, 25,000 sheets of clear printed matters could be obtained.
  • a heat-sensitive lithographic printing plate precursor was prepared in the same manner as in Example 1 except that a polyethylene terephthalate film having a thickness of 0.2 mm was used in place of the aluminum plate in Example 1.
  • the printing plate precursor was subjected to exposure in the same manner as in Example 1. When exposed printing plate precursor was loaded on Harris printer and printing was performed, 10,000 sheets of clear printed matters could be obtained.
  • a hydrophilic layer having the following composition was coated on the substrate having provided thereon the ink-receptive layer used in Example 1, and the coated layer was dried at 100°C for 1 minute, thereby a three dimensionally crosslinked hydrophilic layer having a dry coating weight of about 1 g/m 2 was obtained.
  • a heat-sensitive lithographic printing plate precursor having the same overcoat layer as in Example 6 on the hydrophilic layer was prepared.
  • the printing plate precursor was exposed in the same manner as in Example 1. When the exposed printing plate precursor was loaded on Harris Printer and printing was performed, 20,000 sheets of clear printed matters could be obtained.
  • the coating solution for an ink-receptive layer having the following composition was coated on the same aluminum plate as in Example 1 in a coating amount of 20 ml/m 2 , and the coated layer was dried at 100°C for 1 minute, thereby an aluminum substrate with an ink-receptive layer having a dry coating weight of about 0.6 g/m 2 was obtained.
  • the coating solution for a hydrophilic layer as described below was coated on the ink-receptive layer with a bar coater, and the coated layer was dried at 100°C for 5 minutes, thereby a hydrophilic layer having a dry coating weight of about 2 g/m 2 was obtained.
  • Example 6 The same overcoat layer as in Example 6 was then coated on the hydrophilic layer, thereby a heat-sensitive lithographic printing plate precursor was obtained.
  • This printing plate precursor was attached to 40 W Trend Setter (a plate setter loading a semiconductor laser of 830 nm, 40 W, manufactured by CREO Co., Canada) and exposure was performed by irradiating energy of 600 mJ/cm 2 , and the exposed printing plate precursor was loaded on Harris printer. As a result of printing, 40,000 sheets of clear printed matters could be obtained.
  • 40 W Trend Setter a plate setter loading a semiconductor laser of 830 nm, 40 W, manufactured by CREO Co., Canada
  • hydrophilic resin was used in place of 4 g of a 10% aqueous polyvinyl alcohol solution in Example 18.
  • Example 22 Since the gelation of the coating solution in Example 22 progresses rapidly, coating was immediately completed after mixing the copolymer. Except for that point, each heat-sensitive lithographic printing plate precursor having an overcoat layer was prepared in the same manner as in Example 18, and the printing plate precursor was subjected to exposure. As a result of printing, 40,000 sheets of clear printed matters could be obtained with every printing plate precursor.
  • the present invention can solve the drawbacks of the heat mode plate-making method according to conventional laser exposure. That is, the lithographic printing plate precursor according to the present invention can be loaded on a printer (i.e., a printing press) without necessitating any process after exposure and then printing can be performed as it is.
  • a printer i.e., a printing press
  • a heat-sensitive lithographic printing plate precursor which is excellent in press life and is hard to generate printing staining can be obtained according to the present invention.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Laminated Bodies (AREA)
EP00119409A 1999-09-17 2000-09-12 Précurseur pour plaque lithographique thermosensible Expired - Lifetime EP1084826B1 (fr)

Applications Claiming Priority (2)

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JP26437999A JP2001080226A (ja) 1999-09-17 1999-09-17 感熱性平版印刷版用原板
JP26437999 1999-09-17

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Cited By (3)

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EP1279520A1 (fr) * 2001-07-23 2003-01-29 Fuji Photo Film Co., Ltd. Précurseur de plaque d'impression lithographique
EP1304220A1 (fr) * 2001-10-10 2003-04-23 Fuji Photo Film Co., Ltd. Precurseur de plaque d'impression lithographique thermosensible
EP1291172A3 (fr) * 2001-09-05 2003-08-06 Kodak Polychrome Graphics LLC Un élément multicouche à formation d'image par voie thermique

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EP1541556A4 (fr) * 2002-08-09 2008-03-19 Nippon Kayaku Kk Compose d'indolenine, absorbeur d'infrarouge proche, et toner renfermant cet absorbeur
JP4308687B2 (ja) * 2004-03-11 2009-08-05 富士フイルム株式会社 平版印刷版原版

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WO1994018005A1 (fr) * 1993-02-09 1994-08-18 Agfa-Gevaert Naamloze Vennootschap Matiere d'enregistrement en mode thermique et procede l'utilisant dans la fabrication d'une plaque d'impression lithographique
EP0787583A2 (fr) * 1996-01-30 1997-08-06 Presstek, Inc. Plaques lithographiques avec couches déformables formant coussin
EP0967077A1 (fr) * 1998-06-26 1999-12-29 Agfa-Gevaert N.V. Elément d'enregistrement de l'image et procédé pour la fabrication de plaques lithographiques utilisant cet élément

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EP0620502B1 (fr) * 1993-04-05 1999-03-17 Agfa-Gevaert N.V. Support lithographique et méthode pour la production d'un cliché d'impression lithographique
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EP0580393A2 (fr) * 1992-07-20 1994-01-26 Presstek, Inc. Plaque pour l'impression lithographique
WO1994018005A1 (fr) * 1993-02-09 1994-08-18 Agfa-Gevaert Naamloze Vennootschap Matiere d'enregistrement en mode thermique et procede l'utilisant dans la fabrication d'une plaque d'impression lithographique
EP0787583A2 (fr) * 1996-01-30 1997-08-06 Presstek, Inc. Plaques lithographiques avec couches déformables formant coussin
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EP1279520A1 (fr) * 2001-07-23 2003-01-29 Fuji Photo Film Co., Ltd. Précurseur de plaque d'impression lithographique
EP1464514A1 (fr) * 2001-07-23 2004-10-06 Fuji Photo Film Co., Ltd. Précurseur de plaque d'impression lithographique
US6929895B2 (en) 2001-07-23 2005-08-16 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor
EP1291172A3 (fr) * 2001-09-05 2003-08-06 Kodak Polychrome Graphics LLC Un élément multicouche à formation d'image par voie thermique
EP1304220A1 (fr) * 2001-10-10 2003-04-23 Fuji Photo Film Co., Ltd. Precurseur de plaque d'impression lithographique thermosensible
US6878503B2 (en) 2001-10-10 2005-04-12 Fuji Photo Film Co., Ltd. Heat-sensitive lithographic printing plate precursor

Also Published As

Publication number Publication date
ATE295778T1 (de) 2005-06-15
DE60020196D1 (de) 2005-06-23
EP1084826B1 (fr) 2005-05-18
JP2001080226A (ja) 2001-03-27
DE60020196T2 (de) 2006-01-26
US6852470B1 (en) 2005-02-08

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